Structures and Properties of Novel Multifunctional Hybrid Oligomers†

doi:10.7503/cjcu20141118

Abstract

Abstract:

Tetraglycidyl 4,4'-diaminodiphenylmethane(TGDDM) was toughened by reactive blending and physical blending respectively with multifunctional vinyl ester resin(MVER). Novel multifunctional hybrid oligomer(MVEO-2) containing two different reactive groups was synthesized through the esterfication of TGDDM with acrylic acid(AA)[n(TGDDM)/n(AA)=1∶2] while MVEO_mix was obtained by physical blending TGDDM with MVER. The structures and properties of MVEO-2 and MVEO_mix were studied. FTIR and ¹H NMR show that two oligomers have same structural components. It was found that MVEO_mix presented bimodal and narrow molecular weight distribution while MVEO-2 had multimodal and broad molecular weight distribution. MVEO-2 showed obvious improvement in thermal stability than MVEO_mixfrom thermogravimetric analysis(TGA) and dynamic mechanical analysis(DMA) analysis. The strength and toughness of MVEO-2 were improved than those of MVEO_mix: flexural strength improved 17%, tensile strength improved 38%, elongation improved 35% and impact strength improved 24%. The excellent performance of MVEO-2 was attributed to the formation of close and even interpenetrating polymer network(IPN), which was demonstrated by scanning electron microscope(SEM).

Key words: Reactive blending, Physical blending, Multifunctional oligomer, Hybrid, Thermal stability, Mechanical property

CLC Number:

O631

TrendMD:

QIAN Jianhua, LIU Zuozhen, HUANG Rui, FU Jianhui, CHEN Jianhui, GUO Weihong. Structures and Properties of Novel Multifunctional Hybrid Oligomers^†[J]. Chem. J. Chinese Universities, 2015, 36(5): 996.

Figures/Tables 15

Scheme 1 Structure of TGDDM

Scheme 2 Structures of MVEO-2 and MVER

Fig.1 FTIR spectra of MVEO-2(a), MVEOmix(b), casting of MVEO-2(c) and MVEOmix(d)

Fig.2 1H NMR spectra of MVEO-2(a) and MVEOmix(b)

Fig.3 Molecular weight distributiona. TGDDM; b. MVEO-2; c. MVEOmix; d. MVER.

Table 1 Molecular weight and molecular weight distribution of TGDDM, MVEO-2, MVEOmix and MVER

System	M_n	M_w	Polydispersity index
TGDDM	526	566	1.08
MVEO-2	718	1282	1.79
MVEO_mix	622	861	1.38
MVER	846	1128	1.33

Fig.4 DSC scanning curves of TGDDM/MeTHPA(a),MVEO-2/MEKP/Co/MeTHPA(b),MVEOmix/MEKP/Co/MeTHPA(c)and MVER/MEKP/Co(d)

Table 2 Heat of polymerization and peak temperature for MVEO-2/MEKP/Co/MeTHPA, MVEOmix/MEKP/Co/MeTHPA, MVER/MEKP and TGDDM/MeTHPA

System	Temperature of the peak exotherm/℃	Heat of polymerization/ (J·g^-1)	Calculated heat/ (J·g^-1)
TGDDM	179	431
MVEO-2	85(peak 1), 147(peak 2)	357	389
MVEO_mix	140(peak 1), 171(peak 1)	355	389
MVER	64	347

Table 3 Mechanical properties of TGDDM, MVEO-2 and MVEOmix

System	Flexural strength/ MPa	Flexural modulus/ MPa	Tensile strength/ MPa	Tensile modulus/ MPa	Elongation(%)	Impact strength/ (kJ·m^-2)
TGDDM	111.1	3755	43.2	3650	1.21	7.54
MVEO-2	159.0	3990	62.6	3760	1.71	17.32
MVEO_mix	136.5	4148	45.4	3634	1.27	14.00

Scheme 3 Schematic of cross-linked network for MVEO-2(A) and MVEOmix(B)

Fig.5 TGA curves of MVEO-2(a) and MVEOmix(b)

Fig.6 Variation of E' as a function of temperaturea. TGDDM; b. MVEO-2; c. MVEOmix.

Fig.7 Variation of tanδ as a function of temperaturea. TGDDM; b. MVEO-2; c. MVEOmix.

Table 4 DMTA thermographs for TGDDM, MVEO and MVEOmix

System	T_g(E')/℃	T_g(E″)/℃	T_g(tanδ)/℃
TGDDM	202	217	226
MVEO-2	196	216	224
MVEO_mix	185	205	219

Fig.8 SEM images of TGDDM(A), MVEO-2(B) and MVEOmix(C)

References 29

[1]	Sun M. L., Application Theory and Technology of Epoxy Resin, China Machine Press, Beijing, 2009, 61— 62
	( 孙曼灵. 环氧树脂应用, 北京: 机械工业出版社, 2009, 61— 62)
[2]	Frigione M., E. , Mascia, L. , Acierno, D. , Eur. Polym. J, 1995, 11, 1021- 1029
[3]	Kinloch A., J. , Lee S., H. , Taylor A., C. , Polymer, 2014, 55, 6325- 6334
[4]	Sultania, M. , Yadaw S., B. , Rai J. S., P. , Srivastava, D. , Mater. Sci. Eng., 2010, 527, 4560- 4570
[5]	Scott T., F. , Cook W., D. , Forsythe J., S. , Eur. Polym. J., 2002, 38, 705- 716
[6]	Sperling L. H., Interpenetrating Polymer Networks and Related Materials, Science Press, Beijing, 1987, 1— 10
	( L. H. 斯珀林. 互穿聚合物网络和有关材料. 北京: 科学出版社, 1987, 1— 10)
[7]	Mustata, F. , Tudorachi, N. , Bicu, I. , Compos. Part B, 2013, 55, 470- 478
[8]	Lin M., S. , Liu C., C. , Lee C., T. , J. Appl. Polym. Sci., 1999, 72, 585- 592
[9]	Shaker Z., G. , Browne R., M. , Stretz H., A. , Cassidy P., E. , Blanda M. T., J. , Appl. Polym. Sci., 2002, 84, 2283- 2286
[10]	G B/T 1677-2008, Determination of the Epoxy Value of Plasticizer, Standards Press of China, Beijing, 2008
	( G B/T 1677-2008, 增塑剂环氧值的测定, 北京: 中国标准出版社, 2008)
[11]	GB 2576-2005, Test Method for Insoluble Matter Content of Resin Used in Fiber Reinforced Plastics, Standards Press of China, Beijing, 2005
	( G B/T 2576-2005, 纤维增强塑料树脂不可溶分含量试验方法, 北京: 中国标准出版社, 2005)
[12]	GB/T 2567-2008, Test Methods for Properties of Resin Casting Body, Standards Press of China, Beijing, 2008
	( G B/T 2567-2008, 树脂浇铸体性能试验方法, 北京: 中国标准出版社, 2008)
[13]	Pal, N. , Srivastava, A. , Agrawal, S. , Rai J. S., P. , Mater. Manuf. Process, 2005, 20, 317- 327
[14]	张泽宇. 含环氧基-乙烯基双官能团齐聚物的树脂合成及性能表征, 上海: 华东理工大学, 2014)
	Zhang Z., Y. , Study on Synthesis and Properties of Resins Containing Epoxy-vinylester Bifunctional Oligomers, East China University of Science and Technology, Shanghai, 2014(
[15]	Scala J. J., L. , Orlicki J., A. , Winston, C. , Robinette E., J. , Sands J., M. , Palmese G., R. , Polymer, 2005, 46, 2908- 2921
[16]	Sultnia, M. , Rai J. S., P. , Srivastava, D. , Eur. Polym. J., 2010, 46, 2019- 2032
[17]	Dean, K. , Cook W., D. , Zipper, M. , Burchill, P. , Polymer, 2001, 42, 1345- 1359
[18]	Dean, K. , Cook W., D. , Burchill, P. , Zipper, M. , Polymer, 2001, 42, 3589- 3601
[19]	高玉斌, 刘述梅, 赵建青, 蒋智杰, 袁彦超. 高等学校化学学报, 2014, 35( 2), 396- 401
	Gao Y., B. , Liu S., M. , Zhao J., Q. , Jiang Z., J. , Yuan Y., C. , Chem. J. Chinese Universities, 2014, 35( 2), 396- 401
[20]	Lin M., S. , Chang R., J. , J. Appl. Polym. Sci., 1992, 46, 815- 827
[21]	Lin M., S. , Jeng K., T. , Huang K., Y. , Shih Y. K., J. , Polym. Sci. Polym. Chem. Ed., 1993, 31, 3317- 3325
[22]	Dean K., M. , Cook W., D. , Lin M., Y. , Eur. Polym. J., 2006, 42, 2872- 2887
[23]	Park S., J. , Park W., B. , Lee J., R. , Polym. J., 1999, 31, 28- 31
[24]	Mukherjee C., S. , Saraf M. N., J. , Polym. Sci. Part B: Polym. Phys., 1995, 33, 855- 865
[25]	张铭, 王成忠, 武德珍, 于运花, 杨小平. 高分子材料科学与工程, 2005, 21, 196- 199
	Zhang, M. , Wang C., Z. , Wu D., Z. , Yu Y., H. , Yang X., P. , Polym. Mater. Sci. Eng., 2005, 21, 196- 199
[26]	Cherian A., B. , Varghese L., A. , Thacil E., T. , Eur. Polym. J., 2007, 43, 1460- 1669
[27]	Karikal Chozhan., C. , Rajasekaran, R. , Alagar, M. , Gnanasundaram P., J. , Polym. Mater, 2008, 57, 319- 337
[28]	Tian X., J. , Wang Z., W. , Yu, Q. , Wu Q., Y. , Gao, J. , Chem. Res. Chinese Universities, 2014, 30( 5), 868- 873
[29]	肖善强, 陈其道, 陈明, 洪啸吟. 高等学校化学学报, 2002, 23( 9), 1797- 1800
	Xiao S., Q. , Chen Q., D. , Chen, M. , Hong X., Y. , Chem. J. Chinese Universities, 2002, 23( 9), 1797- 1800